Solid preparations of aryldiazonium fluoborates yielding concentrated diazosolutions and process of making same



Patented June 7, 1932- umrao STATES PArENToFFlcEf f 1mm, scnm'rzsrenmor omnnacn-on-rrm-uem, GERMANY, assrenoa roem;- nm ANILINE wonxs me, or new YORK, 1w. Y., A coaroiwrron or DELAWARE SOLID PREPARATIONS OF ARYLDIAZOlVIUM FLUOIBOR ATES YIELDING CONGEN'IRATED DIAZOSOLUTIONS' AND PROCESS OF MAKING SAME No Drawing. Application filed April 5, 1929, Serial No. 352,896, and in qermany April 8, 1828.

The present invention relates to solid preparations of aryldiazonium. fluoborates yielding concentrated diazosolutions and process of making same.

v The aryldiazonium fluob'orate's' which were first described in the German Patent No. 281,055 and in Ber. dfDeutsch. Chem. Ges., vol. 60, pages 115 and 1186,, show a solubility not. in all cases satisfying the demand of the practice when they are employed as developing salts in dyeing and printing, especially for preparing insoluble dyestuffs on the fiber, i. e. the so-called ice-colors. Stronger diazosolutions than those generally obtainablebymeans of diazonium fluoborates are Y necessary for-the printing process and in the case of dyeing on a standing bath {or replenishing the partially exhausted bath.

I have found that by mixing a-solid and dry diazonium fluoborate with solid salts of metals of the first or third group of the periodic system the metal of which has a greater affinity for the hydrofluoboric acid than for the acid residue of the salt, whereby in some cases diflicultly soluble fluoboric metal saltsmay be separated, mixtures of a good stability are obtained which yield, when only dissolved in water, diazosolutions of a concentration much higher than corresponding to the solubility of the diazonium fiuobo rate employed. Suitable salts to be added for the purpose of the present invention are for example aluminium chloride, alkali metal chlorides or salts or double salts of.

potassium (the acid residue of which forms a more soluble salt with the diazonium compound employed than the fiuoborate residue) Besides the just mentioned ,saltsincreasing the solubility,- other diluents or dyeing expedients may further be present, such assodium sulfate, aluminium sulfate, cupricsulfate or wetting agents.

a The greatand unexpected increase of the. solubility of the diazoniumfluoborates which is effected by my process depends probably upon the fact that the diazonium fluoborates,

exceedingly stable in the dry state, undergo easily a ouble decomposition, when d1s- ---sol ved.in the presence of a salt of the aforesaid kind. Thereby in some cases diflicultly nearly quantitative and as a further advantage of this case the potassium fluoborate' thus separates and may be easily recovered.

"In order to further illustrate my invention the following examples are given, the partsbeing by weight and all temperatures in centrigrade degrees, but'lywish it to be understood that I am not limited to the particular products nor reaction conditions mentioned therein.

Example 1 26 parts of dry 4-nitro-phenyl-1-diazonium fluoborate are mixed with 39 parts or partially dehydrated alum of 140% relating to a molecular weight of 949. The aqueous solution saturated at 20 of this preparation contains 52,5 grs. of paranitraniline relating to a molecular weight of 138 per liter in the form of its diazonium salt. 4 I

Ewample .Z

parts of dry 4-n'itro-phen Ll-diazonium fiuoborate, prepared as descri ed in example 2 of the German specification No. 281055 are mixed with 140 parts of sodium chloride. This 'mixture is introduced at 20 into 600 parts of water. The concentration of the diazo solution thus obtained corresponds to 19,8 grs. para-nitraniline, of molecular weight 138, per liter, whereasthe same fluoborate without the addition of sodium chloride yields a concentration of 10,4grs. of the same base per liter.

By replacing sodium chloride by ammonium chloride diazosolutions are produced the concentration of which corresponds to 22,3 grs. ofpara-nitraniline per'liter.

59 parts of the complex boron-fluorine compoundprepared from diazotized metachloroaniline and sodium fluoborate are inixedwith parts of anhydrous sodium sulfateand 65 parts of potassium sulfate.

This preparation yields when'dissolved in l water a diazo solution which contains at 20 the diazo compound of 24,5 grs. of metachloroaniline of molecular weight 127,5, per liter, whereas only 11 rs. of meta-chloroaniline, of molecular'welght 127,5, per liter can befdissolved at 20 in the form of the diazo compound by starting from an analogous preparation containing no potassium sulfate. i v

Example 4 39 parts of the fiuoborate-of tetrazotized dianisidine, the solubility of which wcorresponds at. 20 to 7,5 grs. of dianisidine, of molecular weight 244, per liter, are mixed with parts of dehydrated sodium-sulfate and 9 parts-of potassium nitrate. The solubility of this preparation in water corresponds at 20 to 45 grs. of the base per liter.

K Example 5 11 parts of 3-nitro-phenyl-1-diazonium-- fluoborate are mixedwith 9 parts of crystallized aluminium chloride and 10 parts of I potassium chloride. This mixture is dissolved in water. "The saturated-solution contains 29,8 grs. meta-nitraniline, of molecular Weight 138, per liter in the form of the diazo compound, whereas the same diazonium fluoborate not containing potassium nor aluminium chloride yields only solutions of the. di'a'zo compound line per liter.

Ea ampZe 6' parts of 3-nitr0-phenyl-1-diazonium fiuoborate are ground with 40 parts of potassium sulfate and 10 parts of partially dehydrated alum. The concentrationof the saturated solution of this preparation corresponds at 20? togrs. of meta-nitraniline, of molecular-weight 138, per-liter:

Iclaim: .1. New preparations consisting of a mixture of a solid aryl diazonium fluoborate of the benzene series with diluting salts, dyeing assistants and with a solid salt of a metal of the first group of the periodic system the metal of which has a greater affinity for the hydrofluoboric acid than for the acid residue ofthe salt. 1

2. New preparations consisting of a mixture of asolid aryl diazonium flu'oborate of the benzene series containing halogen with dlluting salts, dyeing assistants and with a sol1d salt oi a metal of the 'firstgroup of the periodic system themetal of which has a-- greater afiinityfor the-hydrofluoboric' acid thanfor the acid residue of the salt.

3'.'New preparations consisting of a mix- .ture of a solid aryl diazonium fluoborate of the benzene series containing, nitro groups with diluting salts, dyeing assistants and with a solid salt of a metal of the first group has a greater aflinity for the hydrofluoboric 7 acid than for the acid residue of the salt.

' 4. New preparations consisting of a mixture of solid 3-nitro-phenyl-l-diazonium fluoborate with diluting salts, dyeing assistants and with inorganic solid salt of a metal of the first group of the periodic system. the metal of which has a greater aflinity for the hydrofluoboric acid than for the acid residue of the salt. 1

5. New preparations consisting of a mixture of solid 3-nitr0phenyl-1-diazonium fluo-- of 6,5 grs. of meta-nitrani- 

